2-[(1S,4S)-5-methyl-2,5-diazabicyclo[2.2.1]heptan-2-yl]-5-nitrotoluene → 3-Methyl-4-[(1S,4S)-5-methyl-2,5-diazabicyclo[2.2.1]hept-2-yl]aniline

HRID 1875692Notes

Reaction equation

HRID 1875692 reaction equation
[CH3:1][N:2]1[CH2:7][C@@H:6]2[CH2:8][C@H:3]1[CH2:4][N:5]2[C:9]1[CH:14]=[CH:13][C:12]([N+:15]([O-])=O)=[CH:11][C:10]=1[CH3:18]>CCO.[Pd]>[CH3:18][C:10]1[CH:11]=[C:12]([CH:13]=[CH:14][C:9]=1[N:5]1[CH2:4][C@@H:3]2[CH2:8][C@H:6]1[CH2:7][N:2]2[CH3:1])[NH2:15]

Participants

4

Reactant 1

HCID 686324012-[(1S,4S)-5-methyl-2,5-diazabicyclo[2.2.1]heptan-2-yl]-5-nitrotoluene

Product 1

HCID 686333063-Methyl-4-[(1S,4S)-5-methyl-2,5-diazabicyclo[2.2.1]hept-2-yl]anilineYield 93.8%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

2-[(1S,4S)-5-Methyl-2,5-diazabicyclo[2.2.1]hept-2-yl]-5-nitrotoluene (14.2 g), as prepared above in Paragraph D, was dissolved in EtOH (50 mL), transferred to a Parr hydrogenation flask. Pd/C (1.5 g) was introduced to above flask and subjected to hydrogenation at 30 psi for 2 h. The reaction mixture was filtered through Celite and the filter cake was washed further with EtOH (300 mL). Concentration of the filtrate provided 3-Methyl-4-[(1S,4S)-5-methyl-2,5-diazabicyclo[2.2.1]hept-2-yl]aniline as a white-tan solid (11.7 g, 86%); 1H NMR (DMSO-d6): δ 6.58 (d, 1H, J=8.8 Hz), 6.34 (s, 1H), 6.27 (d, 1H, J=8.8 Hz), 4.46 (s, 2H), 3.61 (s, 1H), 3.24 (s, 1H), 3.16 (d, 1H, J=9.3 Hz), 2.93 (dd, 1H, J=1.8 and 9.3 Hz), 2.61 (qt, 2H, J=9.3 Hz), 2.26 (s, 3H), 2.05 (s, 3H), 1.70 (d, 1H, J=9.1 Hz), 1.63 (d, 1H, J=9.1 Hz). LCMS: purity: 97%; MS (m/e): 218 (MH+).

Workup

  1. filtrationThe reaction mixture was filtered through Celite
  2. washthe filter cake was washed further with EtOH (300 mL)

Sources & evidence

ORD record
ord-076eb6c1e5aa4520bbb7c10bf93b7fe2
Source dataset
uspto-grants-2012_11
Patent number
US08309566B2

Reaction notes

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